CN109932467A - Ultra performance liquid chromatography-level four bars/high resolution mass spectrometry measurement Aflatoxin in Peanut byHigh and pesticide residue method - Google Patents
Ultra performance liquid chromatography-level four bars/high resolution mass spectrometry measurement Aflatoxin in Peanut byHigh and pesticide residue method Download PDFInfo
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Abstract
The present invention relates to the detection method more particularly to a kind of ultra performance liquid chromatography-level four bars of a kind of Aflatoxin in Peanut byHigh and pesticide residue/high resolution mass spectrometry measurement Aflatoxin in Peanut byHigh and pesticide residue methods, belong to analytical chemistry field.A kind of method that ultra performance liquid chromatography-level four bars/high resolution mass spectrometry measures 4 kinds of aflatoxin and 11 kinds of pesticide residues in peanut, with high performance liquid chromatography-level four bars-electrostatic field orbit trap high resolution mass spectrum measurement Aflatoxin in Peanut byHigh and pesticide residue, sample is extracted through acetic acidacetonitrile-aqueous extract, PSA and C18 silica gel mixed system purifies, it is eluent gradient elution, high resolution mass spectrum qualitative and quantitative detection that aqueous solution and methanol containing 0.1% formic acid are used under positive ion mode.This method precise and high efficiency, favorable reproducibility while to 4 kinds of aflatoxin in peanut and 11 kinds of pesticide residues, it can be achieved that measure.
Description
Technical field
The present invention relates to the detection methods more particularly to a kind of ultra high efficiency of a kind of Aflatoxin in Peanut byHigh and pesticide residue
The method of 4 kinds of aflatoxin and 11 kinds of pesticide residues, belongs in liquid chromatogram-level four bars/high resolution mass spectrometry measurement peanut
In analytical chemistry field.
Background technique
Peanut is one of the important grain and oil in China and industrial crops, accounts for about the 60% of Peanut total output.The flower in China
Raw and peanut oil total output is held a safe lead in other countries, the world, and becomes the first in the world peanut big export country.With blossoming
The development of raw foreign trade, the TBT (Technical Barriers to Trade) for increasingly importing and exporting mycotoxin and pesticide residue as it,
Therefore challenge is proposed to our detection technique.
Aflatoxin (aflatoxin) has extremely strong toxicity, a kind of tool mainly generated by aspergillus flavus and aspergillus parasiticus
There is a secondary metabolite of bioactivity, humans and animals intake can cause teratogenesis, carcinogenic and mutagenesis, be food safety and public
The one of health is big to be threatened.Aflatoxin is mainly to be generated by the aspergillus flavus and aspergillus parasiticus fungi of aspergillus flavus group, mainly includes
More than 10 kinds of metabolite M1, M2 made of B1, B2, G1, G2 and B1, B2 derive by hydroxylation in vivo etc..Peanut is to be easiest to
By one of the agricultural product of aflatoxin contamination, aspergillus flavus has high compatibility to it, strong carcinogenic due to aflatoxin
Effect, the World Health Organization and various countries all strengthen the detection work to aflatoxin in peanut and its product, and work out
The limitation requirement of harsh aflatoxin B1 and total amount (including B1, B2, G1, G2).Therefore, control the aspergillus flavus poison in peanut
Plain (B1, B2, G1, G2) pollution is of great significance.
Invasion of the peanut in production, transportational process vulnerable to a variety of pest and disease damages, so needing to be subject to using a large amount of pesticide
The phenomenon that preventing and treating, therefore causing excessive pesticide residues in peanut.In recent years, it due to the not scientific amount standard of China's pesticide, causes
China's export peanut is detained and is moved back fortune situation and happened occasionally, and Pesticide Residue has become the outlet of China's peanut after aspergillus flavus poison
Another critical limiting factor after element.
Currently, in peanut aflatoxin detection be broadly divided into enzyme-linked immunization, thin-layered chromatography, high-efficient liquid phase technique and
High performance liquid chromatography-tandem mass method.Detecting Pesticide in peanut is mainly gel permeation chromatography, matrix solid phase dispersion extraction
Take, the methods of QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) is extracted, liquid chromatograph,
Liquid chromatography-tandem mass spectrometry instrument, gas chromatograph, gas chromatography mass spectrometer detection.However these aflatoxin and pesticide are residual
It stays detection method comparatively independent, can not achieve while detecting；It is insufficient to the anti-interference ability of matrix, easily there is false positive.
High resolution mass spectrum (Orbitrap) has the advantages such as high-throughput, highly selective, highly sensitive, and anti-Matrix effects ability is strong, is applicable in
Screening and confirmatory analysis in multiple target compounds.Aflatoxin in Peanut byHigh is detected simultaneously using high resolution mass spectrometry at present
Research with pesticide residue is there is not yet document report.
Summary of the invention
In view of the above problems, the present invention provides a kind of ultra performance liquid chromatography-level four bars/high resolution mass spectrometry measurement flowers
The method of 4 kinds of aflatoxin and 11 kinds of pesticide residues in life.
The technical scheme to solve the above technical problems is that a kind of ultra performance liquid chromatography-level four bars/high score
The method for distinguishing mass spectrometric determination Aflatoxin in Peanut byHigh and pesticide residue, steps are as follows: (1) 4 kinds of aflatoxin and 11 kinds
The preparation of trace standard of pesticide product, (2) peanut sample pre-treatment, (3) liquid chromatographic detection condition: UltiMate 3000 is quick
Liquid chromatograph, Thermo Hypersil Gold C18 column (100mm × 2.1mm, 1.9 μm), 40 DEG C of column temperature, 10 μ of sample volume
L；Mobile phase: A is the aqueous formic acid containing 0.1% (volume fraction), and B is methanol, flow velocity: 0.35mL/min, gradient elution item
Part: 0~0.8min, 2%B；0.8~3min, 2%~24%B；3~4min, 24%B；4~6min, 24%~95%B；6~
9min, 95%B；9~9.5min, 95%~2%B；9.5~12min, 2%B, (4) Mass Spectrometer Method condition: quadrupole rod/electrostatic field
Orbit trap high-resolution mass spectrometer Q-Exactive, heating electric spray ion source (HESI) temperature are 350 DEG C；Capillary voltage is
3.5kV；Ion transfer tube temperature is 320 DEG C；Sheath gas is 40unit, and secondary air speed is 10unit, Full MS/dd-
ms2Scan pattern: acquisition range is 100~600M/Z, cation acquisition；First mass spectrometric resolution ratio is 70 000FWHM, second level
Mass resolution is 17500FWHM；Normalizing collision energy (NCE) is 30eV, 45eV, 60eV, and (5) draw standard curve, (6)
The rate of recovery and precision Procedure experiment.
Preferably, the preparation of aflatoxin and trace standard of pesticide product: configuration mixed standard solution I and hybrid standard are molten
Liquid II, mixed standard solution I include that aflatoxin B1 (AFB1), aflatoxin G 1 (AFG1), pyridine worm narrow, are Acetochlor, more
Bacterium spirit, carbofuran, chlopyrifos, difenoconazole, dimethomorph, imidacloprid, pyrimethanil, Tebuconazole, thiophene worm, mixed standard solution
II includes aflatoxin B 2 and aflatoxin G 2.
Preferably, peanut sample pre-treating method is as follows: sample accurately weighs 2.00g sample and is placed in after crushing and mixing
In polypropylene tool plug centrifuge tube, 10ml acetic acidacetonitrile-aqueous extract (1:84:15, v/v/v) is added, is vortexed and mixes 1min, add
After entering 1.0g magnesium sulfate, 0.3g anhydrous sodium acetate, 1min is shaken immediately, being centrifuged 5min at 4 DEG C with 5000r/min makes solid-liquid point
From 1.0g magnesium sulfate is added in transfer supernatant, 100mg PSA and 400mg C18 silica gel mixed system carries out dispersive solid-phase extraction
Then purification, vortex oscillation 1min are centrifuged 5min in 5000r/min, take 5mL supernatant nitrogen in 40 DEG C of water-baths to be blown to dry, add
Enter methanol-water (50:50, v/v) and be settled to 1ml, after mixing well, crosses 0.22 μm of filter membrane, sample introduction is analyzed.
Preferably, it is as follows to draw standard curve method: using the peanut matrix solution of blank, accurate compound concentration is respectively
1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, the mixed standard solution I of 20 μ g/L and concentration be respectively 0.25 μ g/L, 0.5 μ g/L,
The mixed standard solution II of 1.25 μ g/L, 2.5 μ g/L, 5.0 μ g/L, are detected through high resolution mass spectrum, are vertical with chromatographic peak area (Y)
Coordinate, the mass concentration (X, μ g/L) of contrast solution is that abscissa draws standard curve, full in the range of linearity with each object
Minimum concentration of the sufficient rate of recovery value in 60%~120% section is the quantitative limit of method.
Preferably, the rate of recovery and precision Procedure experiment: take blank peanut sample, add respectively 1 μ g/kg, 2 μ g/kg,
The mixed standard solution I of the 10 various concentration levels of μ g/kg tri-, adds 0.25 μ g/kg, 0.5 μ g/kg, 2.5 μ g/kg tri- respectively
The mixed standard solution II of a various concentration level is measured, each horizontal replication 6 by step (3) and (4) testing conditions
It is secondary, its rate of recovery and relative standard deviation (RSD) are calculated, the rate of recovery of 15 kinds of target compounds is 79.4%~119.8%,
RSD is 4.16~10.23%.
Compared with prior art, the beneficial effects of the present invention are: utilizing high performance liquid chromatography-level four bars-electrostatic field rail
Road trap high resolution mass spectrum is successfully realized 4 kinds of aflatoxin and 11 kinds of pesticide residues while fast qualitative in peanut and quantifies
Analysis.High resolution mass spectrum ensure that the elimination of complex sample mesostroma interference, significantly improve that object is qualitative and quantitative result
Accuracy.The detection method is quick, sensitive, accurate, favorable reproducibility, can meet the day of mycotoxin and pesticide residue in peanut
Often detection demand is suitble to the quick detection of batch samples.
Detailed description of the invention
Fig. 1 is that mixed standard solution I of the present invention and mixed standard solution II extract ion stream chromatogram,
Fig. 2 is the extraction ion stream chromatogram of aflatoxin B1 and chlopyrifos in standard solution,
Fig. 3 is the extraction ion stream chromatogram of aflatoxin B1 and chlopyrifos in positive sample,
Fig. 4 is the second order ms figure of aflatoxin B1 in standard solution,
Fig. 5 is the second order ms figure of aflatoxin B1 in positive sample,
Fig. 6 is the second order ms figure of standard solution Chlorpyrifos,
Fig. 7 is the second order ms figure of positive sample Chlorpyrifos.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment
1 instrument and reagent
(ThermoFisher Scientific is public for quadrupole rod/electrostatic field orbit trap high-resolution mass spectrometer Q-Exactive
Department)；3000 fast liquid chromatography instrument of UltiMate (ThermoFisher Scientific company)；3K15 centrifuge (Germany
Sigma company)；DL-5C low speed large capacity centrifuge (Anting Scientific Instrument Factory, Shanghai)；OA-SYS nitrogen evaporator (the U.S.
ORGANOMATION company)；The ultrapure water purification system of Milli-Q (Millipore company, the U.S.), turbine mixer (German IKA
Company)；Milli-Q ultrapure water (Millipore company, the U.S.)；0.2 μm of PTFE film syringe filters (PALL company).
Aflatoxin B1 (AFB1), aflatoxin B 2 (AFB2), aflatoxin G 1 (AFG1), aflatoxin G 2
(AFG2) standard solution (concentration is 0.5~2 μ g/mL, TRILOGY company)；Pyridine worm narrows, Acetochlor, carbendazim, carbofuran, poison
Dead tick, difenoconazole, dimethomorph, imidacloprid, pyrimethanil, Tebuconazole, Diacloden (Ministry of Agriculture's environmental protection science monitoring
Institute, 1000mg/L)；Acetonitrile, methanol (chromatographically pure, German Merck company)；Formic acid (HPLC grades, Sigma Co., USA)；Acetic acid
(chromatographically pure, Tianjin Ke Miou company)；Anhydrous magnesium sulfate, anhydrous sodium acetate (excellent pure grade, Tianjin Ke Miou company)；PSA filler
(40 μm, Agilent company, the U.S.)；C18 silica gel (40 μm, Agilent company, the U.S.).
2 peanut sample pre-treatments
After sample (38 portions of peanuts) is crushed and (cross 20 meshes) mixing, accurately weighs 2.00g sample and be placed in polypropylene tool plug
In centrifuge tube, 10mL acetic acidacetonitrile-water (1:84:15, v/v/v) extracting solution is added, is vortexed and mixes 1min, 1.0g sulfuric acid is added
After magnesium, 0.3g anhydrous sodium acetate, 1min is shaken immediately, makes to be separated by solid-liquid separation with 5000r/min centrifugation 5min at 4 DEG C.Shift supernatant
1.0g magnesium sulfate is added in liquid, 100mgPSA and 400mg C18 silica gel mixed system carries out dispersive solid-phase extraction purification, vortex oscillation
Then 1min is centrifuged 5min in 5000r/min, takes 5mL supernatant nitrogen in 40 DEG C of water-baths to be blown to dry, methanol-water solution is added
(50:50, v/v) is settled to 1ml, after mixing well, crosses 0.22 μm of filter membrane, sample introduction is analyzed.
The detection of 3 instruments
3.1 instrument testing conditions
3000 fast liquid chromatography instrument of UltiMate (ThermoFisher Scientific company), Thermo
Hypersil Gold C18 column (100mm × 2.1mm, 1.9 μm)；40 DEG C of column temperature；10 μ L of sample volume, mobile phase: A is containing 0.1%
The aqueous solution of the formic acid of (volume fraction), B are methanol, flow velocity: 0.35mL/min, condition of gradient elution: 0~0.8min, 2%B；
0.8~3min, 2%~24%B；3~4min, 24%B；4~6min, 24%~95%B；6~9min, 95%B；9~
9.5min, 95%~2%B；9.5~12min, 2%B.
(ThermoFisher Scientific is public for quadrupole rod/electrostatic field orbit trap high-resolution mass spectrometer Q-Exactive
Department), heating electric spray ion source (HESI) temperature is 350 DEG C；Capillary voltage is 3.5kV；Ion transfer tube temperature is 320
℃；Sheath gas is 40unit, and secondary air speed is 10unit, Full MS/dd-ms2Scan pattern: acquisition range be 100~
600M/Z, cation acquisition；First mass spectrometric resolution ratio is 70 000FWHM, and second order ms resolution ratio is 17500FWHM；Normalization
Collision energy (NCE) is 30eV, 45eV, 60eV.
The optimization of 3.2 chromatographic conditions
3.2.1 the optimization of mobile phase
This experiment has investigated methanol-water, acetonitrile-water, (v/v) aqueous solution of methyl alcohol-formic acid 0.1% respectively as mobile phase,
To the influence that 4 kinds of aflatoxin and 11 kinds of pesticide residue mass spectrums respond, the results show that when using acetonitrile-water as mobile phase, poison
The response of dead tick is obviously relatively low, and under HESI+ ionization mode, the Ionization Efficiency that formic acid improves cation object is added,
Sensitivity and response are further enhanced.Therefore, (v/v) aqueous solution of methyl alcohol-formic acid 0.1% is finally chosen as flowing
Phase, by optimizing gradient elution program, target determinand has obtained optimal separation.Obtain 4 kinds of aflatoxin and 11 kinds of pesticides
Remain the extraction ion stream chromatogram of mixed standard solution.
3.2.2 Mass Spectrometry Conditions optimize
Aflatoxin and pesticide residue are respectively formed in cation scanning process plus hydrogen quasi-molecular ion peak is touching in turn
Fragmentation generates daughter ion when hitting, and wherein aflatoxin can also lose proton in anion scanning process and generate [M-H]?'s
Molecular ion, but response is lower than holotype, therefore is detected using cation scan pattern.It is in resolution ratio (R) first
First mass spectrometric full scan is carried out to 15 kinds of objects under 70 000, by the error of theoretical accurate mass number and actual measurement mass number
Control is in 5ppm (10-6) range, and when parent ion intensity reaches given threshold (1 × 106), automatic trigger second order ms are swept
It retouches, while obtaining the accurate mass number of parent ion and the full scan information of second order ms.Detection obtain 4 kinds of aflatoxin and
The mass spectrometry parameters of 11 kinds of pesticide residues are shown in Table 1.
The mass spectrometry parameters of table 14 kinds of aflatoxin and 11 kinds of pesticide residues
3.2.3 matrix effect
In view of that can have certain matrix effect in sample, this experiment in peanut sample 4 kinds of aflatoxin and
11 kinds of residual matrix effects of agriculture are investigated, and with object in the peak area and solvent in bare substrate liquid peak area
Percentage assesses matrix effect, when result is close to 100%, shows without apparent matrix effect, and being higher than 100% explanation has
Matrix enhancement effect, lower than 100% explanation have substrate inhibition effect.The results show that the matrix effect of 15 kinds of target determinands
Between 60.1%~131.3%, illustrating these types of target detection thing, there are certain matrix enhancement or suppressions in peanut matrix
Effect processed, wherein the matrix enhancement effect of aflatoxin G 1 is stronger, and imidacloprid, clothianidin substrate inhibition effect are stronger.To protect
The accuracy of card method, this experiment carry out quantitative analysis and calculating using the bearing calibration of matrix matching standard solution.
4 draw standard curve
Using the peanut matrix solution of blank, accurate compound concentration is 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L
Aflatoxin B1 (AFB1), aflatoxin G 1 (AFG1), pyridine worm narrow, Acetochlor, carbendazim, carbofuran, chlopyrifos, benzene
Ether methyl cyclic-azole, dimethomorph, imidacloprid, pyrimethanil, Tebuconazole, the serial mixed standard solution I of Diacloden and concentration are 0.25 μ
The series mixing of g/L, 0.5 μ g/L, 1.25 μ g/L, 2.5 μ g/L, the aflatoxin B 2 of 5.0 μ g/L and aflatoxin G 2 are marked
Quasi- solution II, is detected through high resolution mass spectrum, with chromatographic peak area (Y) for ordinate, the mass concentration (X, μ g/L) of contrast solution
Standard curve is drawn for abscissa.High resolution mass spectrum is extracted using the accurate mass number of object, and baseline noise is very low, signal-to-noise ratio
It is often infinitely great, therefore we do not use and determine that the detection limit (LOD) of compound, 10 times of signal-to-noise ratio are true with 3 times of signal-to-noise ratio (S/N)
Determine the method for the quantitative limit (LOQ) of compound, but with reducing spiked levels step by step into blank sample, it is online with each object
Property range in meet minimum concentration of the rate of recovery value in 60%~120% section be method quantitative limit (1imit of
Quantitation, LOQ).The result shows that 4 kinds of aflatoxin and 11 kinds of agricultures it is residual within the scope of respective concentration be in good line
Sexual intercourse, >=0.996,0.25~20 μ g/L of quantitative limit can meet testing requirements to related coefficient (r2).4 kinds of aflatoxin
2 are shown in Table with the range of linearity, linear equation, related coefficient (r2) and the quantitative limit of 11 kinds of pesticide residues.
The range of linearity of 24 kinds of aflatoxin of table and 11 kinds of pesticide residues, linear equation, related coefficient (r2) and quantitative
Limit
5 rate of recovery and precision Procedure experiment: blank peanut sample is taken, adds 1 μ g/kg, 2 μ g/kg, 10 μ g/ respectively
The mixed standard solution I of tri- various concentration levels of kg adds 0.25 μ g/kg, 0.5 μ g/kg, 2.5 μ g/kg, tri- differences respectively
The mixed standard solution II of concentration level, is measured by 3 instrument testing conditions, and each horizontal replication 6 times calculates its rate of recovery
With relative standard deviation (RSD), the rate of recovery of 15 kinds of target compounds be 79.40%~119.8%, RSD be 4.16~
10.23%.The recovery of standard addition and relative standard deviation of 4 kinds of aflatoxin and 11 kinds of pesticide residues are shown in Table 3.
The recovery of standard addition and relative standard deviation (n=6) of 34 kinds of aflatoxin of table and 11 kinds of pesticide residues
6 end-point analysis
38 parts of peanut samples, 5 parts of samples detect aflatoxin B1, and content is 8.14~213.06 μ g/kg, 12 parts of samples
Chlopyrifos is detected, content is 15.38~50.03 μ g/kg.With a peanut sample for detecting aflatoxin B1 and chlopyrifos simultaneously
For product, ion stream chromatogram and second order ms figure are extracted, the qualitative objective determinand compared with the spectrogram of standard solution is passed through.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of ultra performance liquid chromatography-level four bars/high resolution mass spectrometry measurement Aflatoxin in Peanut byHigh and pesticide residue
Method, which is characterized in that steps are as follows: (1) preparation of 4 kinds of aflatoxin and 11 kinds of trace standard of pesticide product, (2) peanut sample
Product processing, (3) liquid chromatographic detection condition: 3000 fast liquid chromatography instrument of UltiMate, Thermo Hypersil Gold
C18 column (100mm × 2.1mm, 1.9 μm)；40 DEG C of column temperature；10 μ L of sample volume, mobile phase: A is the first containing 0.1% (volume fraction)
Aqueous acid, B are methanol, flow velocity: 0.35mL/min, condition of gradient elution: 0~0.8min, 2%B；0.8~3min, 2%~
24%B；3~4min, 24%B；4~6min, 24%~95%B；6~9min, 95%B；9~9.5min, 95%~2%B；
9.5~12min, 2%B, (4) Mass Spectrometer Method condition: quadrupole rod/electrostatic field orbit trap high-resolution mass spectrometer Q-Exactive adds
Thermoelectricity esi ion source (HESI) temperature is 350 DEG C；Capillary voltage is 3.5kV；Ion transfer tube temperature is 320 DEG C；Sheath gas
Flow velocity is 40unit, and secondary air speed is 10unit, Full MS/dd-ms2Scan pattern: acquisition range is 100~600M/Z,
Cation acquisition；First mass spectrometric resolution ratio is 70000FWHM, and second order ms resolution ratio is 17500FWHM；Normalize collision energy
It (NCE) is 30eV, 45eV, 60eV, (5) draw standard curve, (6) rate of recovery and precision Procedure experiment.
2. aspergillus flavus in ultra performance liquid chromatography-level four bars according to claim 1/high resolution mass spectrometry measurement peanut
The method of toxin and pesticide residue, which is characterized in that the preparation of 4 kinds of aflatoxin and 11 kinds of trace standard of pesticide product: configuration
Mixed standard solution I and mixed standard solution II, mixed standard solution I include aflatoxin B1 (AFB1), aflatoxin
G1 (AFG1), pyridine worm narrow, Acetochlor, carbendazim, carbofuran, chlopyrifos, difenoconazole, dimethomorph, imidacloprid, phonetic mould
Amine, Tebuconazole, thiophene worm, mixed standard solution II include aflatoxin B 2 and aflatoxin G 2.
3. aspergillus flavus in ultra performance liquid chromatography-level four bars according to claim 1/high resolution mass spectrometry measurement peanut
The method of toxin and pesticide residue, which is characterized in that peanut sample processing method: sample accurately weighs after crushing and mixing
2.00g sample is placed in polypropylene tool plug centrifuge tube, and 10mL acetic acidacetonitrile-water (1:84:15, v/v/v) extracting solution, whirlpool is added
Rotation mixes 1min, after 1.0g magnesium sulfate, 0.3g anhydrous sodium acetate is added, shakes 1min immediately, is centrifuged at 4 DEG C with 5000r/min
5min makes to be separated by solid-liquid separation, and 1.0g magnesium sulfate is added in transfer supernatant, 100mg PSA and 400mg C18 silica gel mixed system carries out
Then dispersive solid-phase extraction purification, vortex oscillation 1min are centrifuged 5min in 5000r/min, take 5mL supernatant in 40 DEG C of water-baths
Nitrogen be blown to it is dry, be added methanol-water (50:50, v/v) be settled to 1ml, after mixing well, cross 0.22 μm of filter membrane, sample introduction is analyzed.
4. aspergillus flavus in ultra performance liquid chromatography-level four bars according to claim 2/high resolution mass spectrometry measurement peanut
The method of toxin and pesticide residue, which is characterized in that the method for drawing standard curve: quasi- using the peanut matrix solution of blank
True compound concentration is respectively that 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, the mixed standard solution I of 20 μ g/L and concentration are respectively
The mixed standard solution II of 0.25 μ g/L, 0.5 μ g/L, 1.25 μ g/L, 2.5 μ g/L, 5.0 μ g/L, are detected through high resolution mass spectrum, with
Chromatographic peak area (Y) is ordinate, and the mass concentration (X, μ g/L) of contrast solution is that abscissa draws standard curve, with each target
Object meets the quantitative limit that minimum concentration of the rate of recovery value in 60%~120% section is method in the range of linearity.
5. aspergillus flavus in ultra performance liquid chromatography-level four bars according to claim 2/high resolution mass spectrometry measurement peanut
The method of toxin and pesticide residue, which is characterized in that the rate of recovery and precision Procedure experiment: take blank peanut sample, respectively
Add 1 μ g/kg, 2 μ g/kg, 10 μ g/kg, tri- various concentration levels mixed standard solution I, add respectively 0.25 μ g/kg,
The mixed standard solution II of 0.5 μ g/kg, 2.5 μ g/kg, tri- various concentration levels are measured by step (3) and (4) testing conditions,
Each horizontal replication 6 times, calculates its rate of recovery and relative standard deviation (RSD), and the rate of recovery of 15 kinds of target compounds is
79.40%~119.8%, RSD are 4.16~10.23%.
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| CN110618218A (en) * | 2019-11-01 | 2019-12-27 | 国家地质实验测试中心 | Analysis method for rapidly screening pesticide and metabolite residues in tea |
| CN111141843A (en) * | 2019-12-30 | 2020-05-12 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for rapidly determining 14 mycotoxins and 26 pesticide residues in corn |
| CN111141844A (en) * | 2019-12-30 | 2020-05-12 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for rapidly determining 9 mycotoxins and 20 pesticide residues in peanuts |
| CN112034079A (en) * | 2020-09-29 | 2020-12-04 | 中国科学院上海营养与健康研究所 | Novel method for detecting aflatoxin content in tea sample |
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| CN115452997A (en) * | 2022-09-26 | 2022-12-09 | 北京合众恒星检测科技有限公司 | Method for simultaneously detecting forbidden pesticides, mycotoxins and effective components in traditional Chinese medicinal materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229007A (en) * | 1992-04-17 | 1993-07-20 | Agridyne Technologies, Inc. | Selective removal of aflatoxin from azadirachtin containing compositions |
| CN103823008A (en) * | 2014-03-14 | 2014-05-28 | 北京市疾病预防控制中心 | Method for detecting unknown poison by establishing liquid chromatography-mass spectrometry database |
| CN106950298A (en) * | 2017-03-08 | 2017-07-14 | 彭晓俊 | It is a kind of at the same detect Xinhui tangerine peel in mycotoxin and residues of pesticides method |
-
2018
- 2018-08-10 CN CN201810911450.4A patent/CN109932467A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229007A (en) * | 1992-04-17 | 1993-07-20 | Agridyne Technologies, Inc. | Selective removal of aflatoxin from azadirachtin containing compositions |
| CN103823008A (en) * | 2014-03-14 | 2014-05-28 | 北京市疾病预防控制中心 | Method for detecting unknown poison by establishing liquid chromatography-mass spectrometry database |
| CN106950298A (en) * | 2017-03-08 | 2017-07-14 | 彭晓俊 | It is a kind of at the same detect Xinhui tangerine peel in mycotoxin and residues of pesticides method |
Non-Patent Citations (4)
| Title |
|---|
| BARBARA REICHERT ET AL: "Simultaneous determination of 117 pesticides and 30 mycotoxins in raw coffee, without clean-up, by LC-ESI-MS/MS analysis", 《ANALYTICA CHIMICA ACTA》 * |
| M. ANDRASCIKOVA ET AL: "Fast Preconcentration of Pesticide Residues in Oilseeds by Combination of QuEChERS with Dispersive Liquid–Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry", 《FOOD ANAL. METHODS》 * |
| ZBYNEK DZUMAN ET AL: "Multi-analyte high performance liquid chromatography coupled to high resolution tandem mass spectrometry method for control of pesticide residues, mycotoxins, and pyrrolizidine alkaloids", 《ANALYTICA CHIMICA ACTA》 * |
| 高璐斐: "净化液相色谱质谱法快速筛查小麦中污染物方法的建立 ", 《粮食加工》 * |
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